Electrocatalytic process for carbon dioxide conversion

ABSTRACT

An electrocatalytic device for carbon dioxide conversion includes an electrochemical stack comprising a series of cells with a cathode with a Catalytically Active Element metal in the form of supported or unsupported particles or flakes with an average size between 0.6 nm and 100 nm. The reaction products comprise at least one of CO, HCO − , H 2 CO, (HCOO) − , HCOOH, CH 3 OH, CH 4 , C 2 H 4 , CH 3 CH 2 OH, CH 3 COO − , CH 3 COOH, C 2 H 6 , (COOH) 2 , (COO − ) 2 , and CF 3 COOH.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent application Ser. No. 15/724,933 filed on Oct. 4, 2017 (scheduled to issue as U.S. Pat. No. 10,173,169 on Jan. 8, 2019), entitled “Electrocatalytic Process for Carbon Dioxide Conversion”. The '933 application is, in turn, a continuation-in-part of U.S. patent application Ser. No. 15/400,712 filed on Jan. 6, 2017 (now U.S. Pat. No. 9,815,021 issued on Nov. 14, 2017), also entitled “Electrocatalytic Process for Carbon Dioxide Conversion”. The '712 application is, in turn, a continuation-in-part of U.S. patent application Ser. No. 14/684,145 filed on Apr. 10, 2015 (now U.S. Pat. No. 9,555,367 issued Jan. 31, 2017), also entitled “Electrocatalytic Process for Carbon Dioxide Conversion”. The '712 application is also a continuation-in-part of U.S. patent application Ser. No. 15/158,227 filed on May 18, 2016 (now U.S. Pat. No. 9,945,040 issued on Apr. 17, 2018), entitled “Catalyst Layers and Electrolyzers”. The '145 application is, in turn, a division of U.S. patent application Ser. No. 13/445,887 filed on Apr. 12, 2012 (now U.S. Pat. No. 9,012,345 issued on Apr. 21, 2015), entitled “Electrocatalysts for Carbon Dioxide Conversion”. The '887 application is, in turn, a continuation-in-part of U.S. patent application Ser. No. 12/830,338 filed on Jul. 4, 2010, entitled “Novel Catalyst Mixtures”. The '338 application claims priority benefits from U.S. provisional patent application Ser. No. 61/317,955 filed on Mar. 26, 2010, also entitled “Novel Catalyst Mixtures”. The '887 application also claims priority benefits from U.S. provisional patent application Ser. Nos. 61/499,225 filed on Jun. 21, 2011, and 61/540,044 filed on Sep. 28, 2011.

The '933 application is also a continuation-in-part of the '227 application. The '227 application is, in turn, a continuation-in-part of U.S. patent application Ser. No. 14/704,934 filed on May 5, 2015 (now U.S. Pat. No. 9,481,939 issued on Nov. 1, 2016), entitled “Electrochemical Device for Converting Carbon Dioxide to a Reaction Product”. The '934 application is, in turn, a continuation-in-part of international application No. PCT/US2015/14328 filed on Feb. 3, 2015, entitled “Electrolyzer and Membranes”. The '328 international application claims priority benefits, in turn, from U.S. provisional patent application Ser. No. 62/066,823 filed on Oct. 21, 2014. The '934 application is also a continuation-in-part of international application No. PCT/US2015/26507 filed on Apr. 17, 2015, entitled “Electrolyzer and Membranes”. The '507 international application is also a continuation-in-part of the '328 international application and also claims priority benefits from the '823 provisional application.

The '227 application is also a continuation-in-part of U.S. patent application Ser. No. 14/704,935 filed on May 5, 2015 (now U.S. Pat. No. 9,370,773 issued on Jun. 21, 2016), entitled “Ion-Conducting Membranes”. The '935 application is, in turn, a continuation-in-part of the '328 international application and is also a continuation-in-part of the '507 international application.

The '227 application is also a continuation-in part of the '507 international application and is also a continuation-in-part of the '328 international application.

The '227 application also claims priority benefits from the '823 provisional application.

The '227 application is also a continuation-in-part of U.S. patent application Ser. No. 15/090,477 filed on Apr. 4, 2016 (now U.S. Pat. No. 9,580,824 issued on Feb. 28, 2017), entitled “Ion-Conducting Membranes”. The '477 application is, in turn, a continuation-in-part of the '935 application.

Each of the above-identified priority applications is hereby incorporated by reference herein in its entirety.

This application is also related to international application No. PCT/US2011/042809 filed Mar. 25, 2011, entitled “Novel Catalyst Mixtures”, which claims priority benefits from the '338 application, the '098 international application, U.S. provisional patent application Ser. No. 61/484,072 filed May 9, 2011, and U.S. patent application Ser. No. 13/174,365 filed Jun. 30, 2011, all entitled “Novel Catalyst Mixtures”. This application is also related to U.S. provisional patent application Ser. No. 61/499,225 filed on Jun. 29, 2011, entitled “Low Cost Carbon Dioxide Sensors”, and U.S. provisional patent application Ser. No. 61/540,044 filed on Sep. 28, 2011, entitled “On Demand Carbon Monoxide Generator for Therapeutic and Other Applications”.

FIELD OF THE INVENTION

The field of the invention is electrocatalysis and electrocatalysts. The catalysts of this invention are applicable, for example, to the electrochemical conversion of carbon dioxide into useful products.

BACKGROUND OF THE INVENTION

There is a present need to decrease carbon dioxide (CO₂) emissions from industrial facilities. Over the years, a number of electrochemical processes have been suggested for the conversion of CO₂ into useful products. Processes for CO₂ conversion and the catalysts for them are discussed in U.S. Pat. Nos. 3,959,094, 4,240,882, 4,523,981, 4,545,872, 4,595,465, 4,608,132, 4,608,133, 4,609,440, 4,609,441, 4,609,451, 4,620,906, 4,668,349, 4,673,473, 4,711,708, 4,756,807, 4,818,353, 5,064,733, 5,284,563, 5,382,332, 5,457,079, 5,709,789, 5,928,806, 5,952,540, 6,024,855, 6,660,680, 6,987,134, 7,157,404, 7,378,561, 7,479,570, U.S. Patent Application Publication No. 2008/0223727 and papers reviewed by Hori (Modern Aspects of Electrochemistry, 42, 89-189, 2008) (“the Hori Review”), Gattrell, et al. (Journal of Electroanalytical Chemistry, 594, 1-19, 2006) (“the Gattrell review”), DuBois (Encyclopedia of Electrochemistry, 7a, 202-225, 2006) (“the DuBois review”).

Generally, an electrochemical cell contains an anode 50, a cathode 51 and an electrolyte 53 as illustrated in FIG. 1. Catalysts are placed on the anode, and/or the cathode, and/or in the electrolyte to promote desired chemical reactions. During operation, reactants or a solution containing reactants is fed into the cell. Then a voltage is applied between the anode and the cathode, to promote an electrochemical reaction.

When an electrochemical cell is used as a CO₂ conversion system, a reactant comprising CO₂, carbonate or bicarbonate is fed into the cell. A voltage is applied to the cell, and the CO₂ reacts to form new chemical compounds. Examples of cathode reactions in the Hori Review include:

-   CO₂+2e⁻²H⁺→CO+H₂O -   2CO₂+2e⁻→CO+CO₃ ²⁻ -   CO₂+H₂O+2e⁻→CO+2OH⁻ -   CO₂+2H₂O+4e⁻→HCO⁻⁺³OH⁻ -   CO₂+2H₂O+2e⁻→H₂CO+2OH⁻ -   CO₂+H₂O2e^(−→(HCO) ₂)⁻+OH⁻ -   CO₂+2H₂O+2e^(−→H) ₂CO₂+2OH⁻ -   CO₂+5H₂O+6e⁻→CH₃OH+6OH⁻ -   CO₂+6H₂O+8e⁻→CH₄+8OH⁻ -   2CO₂+8H₂O+12e⁻→C₂H₄+12OH⁻ -   2CO₂+9H₂O+12e⁻→CH₃CH₂OH+12OH⁻ -   2CO₂+6H₂O+8e⁻→CH₃COOH+8OH⁻ -   2CO₂+5H₂O+8e⁻→CH₃COO⁻⁺⁷OH⁻ -   2CO₂+10H₂O+14e⁻→C₂H₆+14OH⁻ -   CO₂+2H⁺+2e⁻→CO+H₂O, acetic acid, oxalic acid, oxylate -   CO₂+4H⁺+4e⁻→CH₄+O_(2 where e) ⁻is an electron. The examples given     above are merely illustrative and are not meant to be an exhaustive     list of all possible cathode reactions.

Examples of reactions on the anode mentioned in the Hori Review include:

-   2O²⁻→O₂+4e⁻ -   2CO₃ ²⁻→O₂+2CO₂+4e⁻ -   4OH⁻→O₂+2H₂O+4e⁻ -   2H₂O→O₂+4H⁺+4e⁻     The examples given above are merely illustrative and are not meant     to be an exhaustive list of all possible anode reactions.

In the previous literature, catalysts comprising one or more of V, Cr, Mn, Fe, Co, Ni, Cu, Sn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Ir, Pt, Au, Hg, Al, Si, In, Tl, Pb, Bi, Sb, Te, U, Sm, Tb, La, Ce, and Nd have all shown activity for CO₂ conversion. Reviews include Hori (Modern Aspects of Electrochemistry, 42, 89-189, 2008) (“the Hori Review”), Gattrell, et al. (Journal of Electroanalytical Chemistry, 594, 1-19, 2006) (“the Gattrell review”), DuBois (Encyclopedia of Electrochemistry, 7a, 202-225, 2006) (“the DuBois review”), and the papers Li, et al. (Journal of Applied Electrochemistry, 36, 1105-1115, 2006, Li, et al. (Journal of Applied Electrochemistry, 37, 1107-1117, 2007, and Oloman, et al. (ChemSusChem, 1, 385-391, 2008) (“the Li and Oloman papers”), and references therein.

The results in the Hon Review show that the conversion of CO₂ is only mildly affected by solvent unless the solvent also acts as a reactant. Water can act like a reactant, so reactions in water are different than reactions in non-aqueous solutions. But the reactions are the same in most non-aqueous solvents, and importantly, the overpotentials are almost the same in water and in the non-aqueous solvents.

The catalysts have been in the form of either bulk materials, supported particles, collections of particles, small metal ions or organometallics. Still, according to Bell (A. Bell. Ed, Basic Research Needs, Catalysis For Energy, U.S. Department of Energy Report PNNL17712, 2008) (“the Bell Report”), “The major obstacle preventing efficient conversion of carbon dioxide into energy-bearing products is the lack of catalyst” with sufficient activity at low overpotentials and high electron conversion efficiencies.

The overpotential is associated with lost energy of the process, so the overpotential should be as low as possible. Yet, according to The Bell Report “Electron conversion efficiencies of greater than 50 percent can be obtained, but at the expense of very high overpotentials”. This limitation needs to be overcome before practical processes can be obtained.

A second disadvantage of many of the catalysts is that they also have low electron conversion efficiency. Catalyst systems are considered practical where electron conversion is over 50%.

U.S. patent application Ser. Nos. 12/830,338 and 13/174,365 (published as US2012/0308903), International Application No. PCT/US2011/030098 (published as WO2011/120021) and PCT/US2011/042809 (published as WO2012/006240) disclose that a catalyst mixture containing an active metal and a Helper Catalyst could catalyze CO₂ conversions with low overpotential and high electron conversion efficiency. However, the catalysts disclosed in these patent applications showed a lower activity than was desired.

The patent documents identified above consider applications for CO₂ conversion, but the present electrocatalysts overcome limitations of other systems. For example, some commercial CO₂ sensors use an electrochemical reaction to detect the presence of CO₂. At present, these sensors require over 1-5 watts of power, which is too high for portable sensing applications.

SUMMARY OF THE INVENTION

The present process employs a novel catalyst combination that can overcome one or more of the limitations of low rates, high overpotentials and low electron conversion efficiencies (namely, selectivities), low rates for catalytic reactions and high power requirements for sensors. The catalyst combination or mixture includes at least one Catalytically Active Element in the form of supported or unsupported particles wherein the particles have an average particle size (as defined below) between about 0.6 nm and 100 nm, preferably between 0.6 nm and 40 nm, and most preferable between 0.6 nm and 10 nm. The catalyst combination also includes a Helper Polymer that can contain, for example, positively charged cyclic amine groups, such as imidazoliums or pyridiniums. The catalyst combination of a Catalytically Active Element and a Helper Polymer is useful, for example, in the cathode catalyst layer of an electrochemical cell used for conversion of CO₂ to various reaction products.

An electrochemical device for carrying out the foregoing process can include a stack comprising at least two electrochemical cells electrically connected in series with the anode of one cell in the stack in electrical contact with the cathode from a different cell in the stack.

Preferably, the stack includes (i) a means to provide liquid electrolyte to the anode of each of the cells, (ii) a means to provide gaseous CO₂ to the cathodes of each of the cells, and (iii) a membrane interposed between the anode and cathode in each of the cells.

Preferably, the minimum ion conduction path between adjacent anodes is at least 3 cm.

Preferably, the minimum ion conduction path between adjacent anodes is at least 10 times the membrane thickness, most preferably at least 100 times the membrane thickness.

The present process is not limited to catalysts for CO₂ conversion. In particular, catalysts that include Catalytically Active Elements and Helper Catalysts or Helper Polymers might enhance the rate of a wide variety of chemical reactions. Reaction types include: homogeneously catalyzed reactions, heterogeneously catalyzed reactions, chemical reactions in chemical plants, chemical reactions in power plants, chemical reactions in pollution control equipment and devices, chemical reactions in fuel cells, and chemical reactions in sensors. The present process includes all of these examples.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of a typical electrochemical cell.

FIG. 2 illustrates how the cyclic voltammogram (CV) of electrochemical water reduction varies with the average particle size of the Catalytically Active Element silver on the cathode: (A) bare silver electrode, (B) electrode covered by nominally 200 nm silver particles, (C) electrode covered by nominally 100 nm silver particles, (D) electrode covered by nominally 20-40 nm silver particles, (E) electrode covered by 5 nm silver particles, and (F) electrode covered by 0.67 nm silver particles. The numeric designations 500-505 indicate the positions of the hydrogen peak in the figures. All of the CV's are reported as the current divided by the electrochemical surface area of the particles

FIG. 3 illustrates how the CV changes in FIG. 2 when CO₂ is added to the reaction: (A) bare silver electrode, (B) electrode covered by nominally 200 nm silver particles, (C) electrode covered by nominally 100 nm silver particles, (D) electrode covered by nominally 20-40 nm silver particles, (E) electrode covered by 5 nm silver particles, and (F) electrode covered by 0.67 nm silver particles. The numeric designations 600-605 indicate the CO₂ reduction peak in the figures. All of the CV's are reported as the current divided by the electrochemical surface area of the particles

FIG. 4 illustrates particle size distribution of the (A) nominally 20-40 nm silver particles, (B) nominally 100 nm silver particles, and (C) nominally 200 nm silver particles as measured by dynamic light scattering. The nominally 20-40 nm particles have an average size of 35 nm. The nominally 100 nm particles have an average size of 70 nm and the nominally 200 nm particles have an average size of 190 nm.

FIG. 5 shows how the voltammograms of a 5 cm² cell change when 0% (plot 200), 1% (plot 201), 5% (plot 202), and 10% (plot 203) of Helper Polymer PSMIMCl are added to the CO₂ electrolyzer cathode catalyst layer, where the percentage is calculated as the weight of the PSMIMCl divided by the weight of the silver. “PSMIMCl” refers to the chloride form of a co-polymer of polystyrene and poly 1-(p-vinylbenzyl)-3-methyl-imidazolium.

FIG. 6 illustrates an embodiment of the stacks described herein, which comprise two or more electrochemical cells, each of which consists of an anode, a cathode, a membrane interposed between the anode and the cathode, and an electrical connection between cells.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENT(S)

The invention disclosed herein is not limited to the particular methodology, protocols, and reagents described herein, as these can vary as persons familiar with the technology involved here will recognize. The terminology employed herein is used for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention. As used herein and in the appended claims, the singular forms “a,” “an,” and “the” include the plural reference unless the context clearly dictates otherwise. Thus, for example, a reference to “a linker” is a reference to one or more linkers and equivalents thereof known to persons familiar with the technology involved here.

Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by persons familiar with the technology involved here. The embodiments of the invention and the various features and advantageous details thereof are explained more fully with reference to the non-limiting embodiments and/or illustrated in the accompanying drawings and detailed in the following description, where the term “and/or” signifies either one or both of the options. It should be noted that the features illustrated in the drawings are not necessarily drawn to scale, and features of one embodiment can be employed with other embodiments as persons familiar with the technology involved here would recognize, even if not explicitly stated herein.

Any numerical value ranges recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least two units between any lower value and any higher value. As an example, if it is stated that the concentration of a component or value of a process variable such as, for example, size, angle size, pressure, time and the like, is, for example, from 1 to 90, specifically from 20 to 80, more specifically from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32, and so on, are expressly enumerated in this specification. For values which are less than one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value are to be treated in a similar manner.

Moreover, provided immediately below is a “Definitions” section, where certain terms related to the invention are defined specifically. Particular methods, devices, and materials are described, although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the invention. All references referred to herein are incorporated by reference herein in their entirety.

Definitions

The term “electrochemical conversion of CO₂” as used here refers to any electrochemical process where carbon dioxide, carbonate, or bicarbonate is converted into another chemical substance in any step of the process.

The term “CV” as used here refers to a cyclic voltammogram or cyclic voltammetry.

The term “Overpotential” as used here refers to the potential difference (voltage) between a reaction's thermodynamically determined reduction or oxidation potential and the potential at which the event is experimentally observed.

The term “Cathode Overpotential” as used here refers to the overpotential on the cathode of an electrochemical cell.

The term “Anode Overpotential” as used here refers to the overpotential on the anode of an electrochemical cell.

The term “Electron Conversion Efficiency” refers to selectivity of an electrochemical reaction. More precisely, it is defined as the fraction of the current that is supplied to the cell that goes to the production of a desired product.

The term “Catalytically Active Element” as used here refers to any chemical element that can serve as a catalyst for the electrochemical conversion of CO_(2.)

The term “Helper Catalyst” as used here refers to any organic molecule or ion, or a mixture of organic molecules and/or ions, that does at least one of the following:

-   -   (a) Speeds up a chemical reaction; or     -   (b) Lowers the overpotential of the reaction,         without being substantially consumed in the process.

The term “Helper Polymer” as used here refers to a polymer that does at least one of the following:

-   -   (a) Speeds up a chemical reaction;     -   (b) Increases the current seen in an electrochemical reaction at         a given potential;     -   (c) Increases the Faradaic efficiency of a given reaction; or     -   (d) Increases the selectivity of a reaction.

The term “MEA” as used here refers to a membrane electrode assembly.

The term “imidazolium” as used here refers to a positively charged ligand containing an imidazole group. This includes a bare imidazole or a substituted imidazole. Ligands of the form:

where R₁-R₅ are each independently selected from hydrogen, halogens, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, cyclic aryls, heteroaryls, alkylaryls, heteroalkylaryls, and polymers thereof, such as the vinyl benzyl copolymers described herein, are specifically included.

The term “pyridinium” as used here refers to a positively charged ligand containing a pyridinium group. This includes a protonated bare pyridine or a substituted pyridine or pyridinium. Ligands of the form:

where R₆-R₁₁ are each independently selected from hydrogen, halogens, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, cyclic aryls, heteroaryls, alkylaryls, heteroalkylaryls, and polymers thereof, such as the vinyl benzyl copolymers described herein, are specifically included.

The term “pyrazoliums” as used here refers to a positively charged ligand containing a pyrazolium group. This includes a bare pyrazolium or a substituted pyrazolium. Ligands of the form:

where R₁₆-R₂₀ are each independently selected from hydrogen, halogens, linear alkyls, branched alkyls, cyclic alkyls, heteroalkyls, aryls, cyclic aryls, heteroaryls, alkylaryls, heteroalkylaryls, and polymers thereof, such as the vinyl benzyl copolymers described herein, are specifically included.

The term “phosphonium” as used here refers to a positively charged ligand containing phosphorous. This includes substituted phosphorous. Ligands of the form:

-   -   P⁺(R₁₂R₁₃R₁₄R₁₅)         where R₁₂-R₁₅ are each independently selected from hydrogen,         halogens, linear alkyls, branched alkyls, cyclic alkyls,         heteroalkyls, aryls, cyclic aryls, heteroaryls, alkylaryls,         heteroalkylaryls, and polymers thereof, such as the vinyl benzyl         copolymers described herein, are specifically included.

The term “positively charged cyclic amine” as used here refers to a positively charged ligand containing a cyclic amine. This specifically includes imidazoliums, pyridiniums, pyrazoliums, pyrrolidiniums, pyrroliums, pyrimidiums, piperidiniums, indoliums, triaziniums, and polymers thereof, such as the vinyl benzyl copolymers described herein.

The term “polymer electrolyte membrane” refers to both cation exchange membranes, which generally comprise polymers having multiple covalently attached negatively charged groups, and anion exchange membranes, which generally comprise polymers having multiple covalently attached positively charged groups. Typical cation exchange membranes include proton conducting membranes, such as the perfluorosulfonic acid polymer available under the trade designation NAFION from E.I. du Pont de Nemours and Company (DuPont) of Wilmington, Del.

The term “anion exchange membrane” as used here refers to membranes comprising polymers wherein said polymers comprise positively charged groups.

The term “stack” as used here refers to a plurality of electrochemical cells connected in series.

The term “ion conduction path” as used here is the path that ions can take from one cell to another in a stack without the ions going through the membranes separating the anode and the cathode in any cell.

SPECIFIC DESCRIPTION

The present process relates generally to Catalytically Active Element, Helper Polymer Mixtures where the mixture does at least one of the following:

-   -   (a) Speeds up a chemical reaction;     -   (b) Increases the current seen in an electrochemical reaction at         a given potential;     -   (c) Increases the Faradaic efficiency of a given reaction; or     -   (d) Increases the selectivity of a reaction.

For example, such mixtures can increase the rate of CO₂ conversion to a value that is higher than when the same Catalytically Active Element is used without the Helper Polymer.

U.S. patent application Ser. Nos. 12/830,338, 13/174,365, and International Application No. PCT/US2011/030098 (published as

WO2011/120021) and PCT/US2011/042809 (published as WO2012/006240) disclose that a catalyst mixture containing a Catalytically Active Metal and a Helper Catalyst catalyzes CO₂ conversions with low overpotential and high electron conversion efficiency. Active Metals included one or more of V, Cr, Mn, Fe, Co, Ni, Cu, Sn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Ir, Pt, Au, Hg, Al, Si, In, Tl, Pb, Bi, Sb, Te, U, Sm, Tb, La, Ce, and Nd. Examples of Helper Polymers include polymers containing one or more of positively charged cyclic amines, phosphines, imidazoliums, pyridiniums, pyrrolidiniums, phosphoniums, sulfoniums, prolinates, methioninates, cholines, acetylcholines, alanines, aminoacetonitriles, methylammoniums, arginines, aspartic acids, threonines, chloroformamidiniums, thiouroniums, quinoliniums, pyrrolidinols, serinols, benzamidines, sulfamates, acetates, carbamates, triflates, and cyanides.

Of course, the '338 U.S. application, the '365 U.S. application, the '098 international application and the '809 international application disclose that not every substance listed above will act as a Helper Polymer. In general, one can determine whether a polymer P is a Helper Catalyst for electrochemical conversion of CO₂ catalyzed by a catalytically active element M by the following test:

-   -   (1) Prepare two different membrane electrode assemblies (MEAs)         with 5 cm² of active area: (i) one having the polymer P in the         cathode catalyst layer; and (ii) one otherwise identical but         without the polymer P in the cathode catalyst layer, wherein the         weight of the polymer is 4% of the weight of the catalytically         active element M.     -   (2) Both membrane electrode assemblies are mounted in Fuel Cell         Technologies (Albuquerque, N. Mex.) 5 cm² fuel cell hardware         assembly with serpentine flow fields.     -   (3) CO₂ humidified at 50° C. is fed into the cathode of both         cells at a rate of 5 sccm with the cell at room temperature and         pressure, and the anode side is left open to the atmosphere at         room temperature and pressure.     -   (4) A voltage of 1 V is applied to the cell without the polymer         P, and then the voltage is raised to a voltage V such that the         output current is as least 20 mA/cm². The current output of the         cell is recorded after running for 30 minutes.     -   (5) The same voltage V is applied to the cell with the polymer P         and the current output of the cell is recorded after running for         30 minutes.         If the current is at least 20% higher in the cell with the         polymer P in the catalyst layer than the cell without the         polymer P in the catalyst layer, the polymer P is a Helper         Polymer for that reaction.

Preferably the two MEA's are manufactured as follows:

-   -   (1) A solvent S is identified such that S can dissolve at least         5 mg of the polymer P in 3 mL of solution.     -   (2) A cathode for the MEA containing the polymer P is prepared         as follows:         -   (a) 100 mg of nanoparticles of Catalytically Active Element             M are mixed with 4 mg of polymer P, and 3 mL of solvent S.         -   (b) The mixture is sonicated for 10 minutes to create a             catalyst ink.         -   (c) The ink is painted onto a gas diffusion layer (Sigracet             35 BC GDL, Ion Power Inc., New Castle, Del.) covering an             area of 6 cm×6 cm. The electrode was immersed in 1 M KOH for             at least 1 hour for ion exchange, then the electrode is cut             into 2.5 cm×2.5 cm sections for cell testing.     -   (3) The anode for the MEA is prepared as follows:         -   (a) 100 mg of IrO₂ (43396, Alfa Aesar, Ward Hill, Mass.) is             dispersed in the mixture of 1 ml of deionized water, 2 ml of             isopropanol (3032-16, Macron Fine Chemicals, Avantor             Performance Materials, Center Valley, Pa.) and 0.1 ml of 5             wt. % poly-tetrafluoroethylene (PTFE) dispersion (665800,             Sigma-Aldrich, St. Louis, Mo.).         -   (b) The mixture is sonicated for 10 min using a water bath             sonicator.         -   (c) The ink is painted onto 6 cm×6 cm of carbon fiber paper             (Toray Paper 120, Fuel Cell Earth, Woburn, Mass.). The IrO₂             loading is about 2 mg/cm². The electrode is cut into 3 cm×3             cm sections for cell testing.     -   (4) An anion exchange membrane is sandwiched between the anode         and the cathode with the metal-containing layers on the anode         and cathode facing the membrane to create the MEA. Preferably         the anion exchange membrane is one of the helper membranes         described in U.S. Pat. No. 9,370,773.     -   (5) The same procedure is used to create the MEA the does not         contain the Polymer, except no polymer P is added in step 2a.

In the foregoing applications, new catalyst formulations are disclosed that maintain the ability to convert CO₂ with a high electron conversion efficiency and low overpotential, but also show an improved specific catalytic activity. The catalyst of the present application was prepared by modifying the structure of the silver so it is more active. The catalyst can be in the form of supported or unsupported metal particles wherein the average particle size is below about 100 nm, preferably between 0.6 nm and 40 nm, more preferably between 0.6 nm and 20 nm, and most preferably between 0.6 nm and 10 nm.

In this context, the particle sizes can be determined by one or more of microscopy, x-ray line broadening, chemisorption, or small angle x-ray scattering. For example, one might measure the x-ray diffraction pattern of the catalysts, determine β the width of the diffraction line at some angle θ and then calculate the particle size, D, from the Scherrer equation:

$D = \frac{0.9\mspace{11mu}\lambda}{\beta\mspace{11mu}{\cos(\theta)}}$ where λ is the wavelength of the x-ray beam.

Chemisorption can alternately be used to measure the S_(g), the surface area of the active element per unit mass, and then calculate the particle size from the formula:

$D = \frac{5}{S_{g}\rho}$ where p is the bulk density of the active element.

The present process specifically includes any catalyst with a particle size between 0.6 nm and 100 nm measured by any of x-ray line broadening, chemisorption, or small angle x-ray scattering.

BACKGROUND DATA An Illustration of the Effects of Particle Size on CO₂ Conversion on a Silver/EMIM Catalyst

Catalysts Tested

This example illustrates the effect of silver particle size on the rate of CO₂ conversion on an EMIM-BF4 (Sigma Aldrich, St. Louis, Mo.) coated silver catalyst.

Experimental Data

During the experiments, a silver ink was deposited onto a silver rotating disk electrode (Pine Instruments, Grove City, Pa.). In the first experiment, the silver electrode was polished, and a CV was run as described in the fourth paragraph below. Subsequent experiments were run by depositing one of: (i) 200 nm silver (Sigma Aldrich, St. Louis, Mo.); (ii) 100 nm silver (Sigma Aldrich); (iii) 20-40 nm silver (Sigma Aldrich); (iv) 5 nm (UT Dots, Champaign, Ill.); (v) 0.67 nm (Purest Colloids, Westampton, N.J.) onto the silver electrode and running the CV as set forth in the fourth paragraph below.

In the case of 500-1000 nm, 100 nm, and 20-40 nm silver, a silver ink was prepared by mixing 5.6 mg of silver particles with 1 ml deoxygenated Millipore water. The catalyst was applied on the surface of a rotating electrode by adding 60 μL of the ink to the surface and allowing the water to evaporate under ambient temperature for 60 minutes. In order to ensure the quality of the measurements, special attention was paid to the material cleaning and solution purity.

The 10 nm Ag arrived suspended in an organic solution, so this solution was applied to the silver electrode, and subsequently heated in air at 85° C. for 3 hours to remove residual organics.

The 0.6 nm Ag particles arrived suspended in distilled water, so they were used as received.

The counter electrode was made by attaching a 25 mm×25 mm platinum mesh (size 52) to a 5-inch platinum wire (99.9%, 0.004-inch diameter). A silver quasi-reference electrode (Ag-QRE) was used. The electrolytes were first loaded into the glass cell and then purged with dry argon (99.99%) for two hours in order to remove oxygen from the electrolytes. Prior to each experiment, a 20-40 linear sweep cyclic voltammogram at 75 mVs⁻¹ was taken with the range between −2 V and 0 vs.

Ag-QRE in order to condition the electrodes and remove oxides from the surfaces. Then several cycles were performed at 10 mVs⁻¹ before taking the final cycle to ensure that the CV had stabilized (that is, any “dirt” or other material was removed from the surfaces). Finally, cleaning and stabilizing CV cycles were performed at 10 mVs⁻¹. Then CO₂ was bubbled in the solution at 1 atm pressure for 20 minutes. Cyclic voltammetry was conducted again at a sweep rate of 10 mV/s in the range from −2 V to 0 V vs. Ag-QRE. Results: Water Electrolysis

FIG. 2 shows how the CV of water varies with particle size. One finds that there is very little variation in the catalytic activity of silver, in agreement with the literature reviewed in a recent paper, M.T.M. Koper, “Structural sensitivity and nanostructure effects in electrocatalysis”, Nanoscale 3, 2054 (2011) (“the Koper Paper”).

Results: CO₂ Electrolysis

FIG. 3 shows how the CV changes when CO₂ is added to the electrochemical cell. Notice that CO₂ conversion peaks, labeled 100, 101, 102, 103, 104, 105 and 106 are observed. The CO₂ conversion peaks grow as one decreases the particle size from 1000-10 nm, but then we observed the opposite effect, where the CO₂ peak shrinks moving from 10 nm to 0.6 nm. Evidently, there is an optimal particle size somewhere between 0.6 and 100 nm. The optimal size is probably between 0.6 and 40 nm, most probably between 0.6 and 20 nm.

The result above shows that unsupported silver catalysts have an optimal size between 0.6 and 100 nm. Those familiar with the technology involved here know that if a reaction is structure sensitive on an unsupported catalyst, or single crystal, it will also show structure sensitivity on a supported catalyst. Further, the Koper paper suggests that if a reaction is structure sensitive on one transition metal, it will also be structure sensitive on most other transition metals. In particular, the optimum particle size is very similar on most transition metals. Therefore, we conclude that V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, W, Re, Ir, Pt, Au, Hg, Pb and Bi electrocatalysts for CO₂ conversion should have an optimal particle size between 0.6 and 100 nm.

Example 1: Use of Solid Polymers as Helper Catalysts

The objective of this example is to show that polymers containing imidazoliums can be Helper Catalysts.

A copolymer, which is designated here as PSMIM (Cl), was prepared following the synthetic route in U.S. Pat. No. 9,370,773. “PSMIM” refers to a co-polymer of polystyrene and poly 1-(p-vinylbenzyl)-3-methyl-imidazolium:

where X⁻is an anion, m>0 and n>0.

The inhibitor-free styrene was prepared by passing styrene (Sigma-Aldrich) through the tert-butylcatechol (TBC) inhibitor remover (Sigma-Aldrich 311340). In general, 40 ml of remover is sufficient to yield 50 ml of clear, inhibitor free styrene. Inhibitor TBC in 4-vinylbenzyl chloride (4-VBC) was removed by the same inhibitor remover in a similar fashion.

Poly(4-vinylbenzyl chloride-co-styrene) was then synthesized by heating a solution of inhibitor-free styrene (Sigma-Aldrich) (36.139 g, 350 mmol) and 4-vinylbenzyl chloride (Sigma-Aldrich) (29.7272 g, 190 mmol) in chlorobenzene (Sigma-Aldrich) (45 ml) at 60-65° C. in an oil bath for approximately 20 hours under argon gas with AIBN (α,α′-Azoisobutyronitrile, Sigma-Aldrich) (0.5927 g, 0.90 wt % based on the total monomers' weight) as initiator. The copolymer was precipitated in CH₃OH (methanol) and dried under vacuum.

“4-VBC-co-St” or “poly(4-vinylbenzyl chloride co-styrene)” as used here refers to a co-polymer of styrene and 4-vinylbenzyl chloride:

where m>0 and n>0.

“Polystyrene methyimidazolium chloride” (PSMIM-Cl) was synthesized by adding 1-methylimidazole (Sigma-Aldrich) (2.8650 g, 034.9 mmol), which is an alkylimidazole, to the solution of the poly(4-VBC-co-St) (5.0034 g, 19.4 mmol) in anhydrous N,N-Dimethylformamide (DMF) (Sigma-Aldrich) (30 mL). The mixture was then stirred at around 30° C. for around 50 hours to form a PSMIM solution.

“4-VBC-co-St” or “poly(4-vinylbenzyl chloride co-styrene)” as used here refers to a co-polymer of styrene and 4-vinylbenzyl chloride:

where m>0 and n>0.

Anion exchange membrane polymer PSMIM-DVB was synthesized starting with poly(4-vinylbenzyl chloride co-styrene.) 1-methylimidazole (Sigma-Aldrich) (3.912 g, 47.7 mmol) was added in a 250 ml 3-neck round bottom flask to the solution of the poly(4-VBC-co-St) (15.358 g, 59.8 mmol) in anhydrous N,N-Dimethylformamide (DMF) (Sigma-Aldrich) (105 ml). 0.22 ml of a divinylbenzene (DVB) in DMF solution (DVB concentration=0.0083 g/ml) was carefully added through a pipette to the mixture with continual magnetic stirring. After this, 0.22 ml of AIBN-DMF solution (AIBN concentration=0.0083 g/ml) was added to the mixture in a similar fashion. The reaction was then kept under nitrogen atmosphere at 50° C. for about 60 hours. PSMIM-DVB was obtained as a white powder after purification by precipitation into diethyl ether.

Membranes were prepared by casting the PSMIM-DVB solution prepared above directly onto a flat glass surface. The thickness of the solution on the glass was controlled by a film applicator (MTI Corporation, Richmond, Calif.) with an adjustable doctor blade. The membranes were then dried in a vacuum oven in the following stepwise fashion. They were first kept at 80° C. for 120 minutes, then at 100° C. for 60 minutes, at 120° C. for 30 minutes and finally at 150° C. for 60 minutes. Chloride ions in the membranes were removed by soaking the membranes in 1 M KOH solution for 24 hours or longer.

The cathode layer in Example 1 was prepared as follows. Silver ink was made by mixing 100 mg of silver nanoparticles (20-40 nm, 45509, Alfa Aesar, Ward Hill, Mass.), 5 mg porous carbon (Vulcan XC-72R, Fuel Cell Earth, Woburn, Mass.) and different amounts of PSMIM-Cl in 3 ml of ethanol (459844, Sigma-Aldrich). The mixture was then sonicated for 10 minutes. The silver ink was painted onto a gas diffusion layer (Sigracet 35 BC GDL, Ion Power Inc., New Castle, Del.) covering an area of 6 cm×6 cm. The electrode was immersed in 1 M KOH for at least 1 hour so that PSMIM-Cl converted by ion exchange to PSMIM-OH. Then the electrode was cut into 2.5 cm×2.5 cm sections for cell testing.

The anode in Example 1 was prepared as follows: 100 mg of IrO₂ (43396, Alfa Aesar) was dispersed in the mixture of 1 ml of deionized water, 2 ml of isopropanol (3032-16, Macron Fine Chemicals, Avantor Performance Materials, Center Valley, Pa.) and 0.1 ml of 5 wt. % poly-tetrafluoroethylene (PTFE) dispersion (665800, Sigma-Aldrich). The mixture was sonicated for 10 min using a water bath sonicator. The ink was painted onto 6 cm×6 cm of carbon fiber paper (Toray Paper 120, Fuel Cell Earth). The actual IrO₂ loading was about 2 mg/cm². The electrode was cut into 3 cm×3 cm sections for cell testing.

The PSMIM-DVB membrane was sandwiched between the anode and the cathode with the metal-containing layers on the anode and cathode facing the membrane, and the whole assembly was mounted in a Fuel Cell Technologies 5 cm² fuel cell hardware assembly with serpentine flow fields configured as in FIG. 1 with an anode gas chamber 50, an anode 51, a membrane 52, a cathode 53, cathode gas chamber 54, a means to make a connection with the cathode 55, a means to make a connection to the anode 56. The figure also shows a source of potential to device 57. In the experiments reported here that source was a potentiostat although many other power supplies could be used.

CO₂ humidified at 25° C. was fed into the cathode flow field at a rate of 20 sccm, and 10 mM KHCO₃ was fed into the anode flow field. The cyclic voltammograms were collected by scanning the cell voltage from 1.2 to 3.0 V. All of the scans were made at room temperature and atmospheric pressure.

FIG. 5 shows the results of the above scans. Plot 200 is a base case with no PSMIM in the cathode catalyst layer ink. It should be noted that the current increases when PSMIM is added to the catalyst layer in a later sample, such that the PSMIM weight is 1% of the weight of the silver (plot 201). Further increases in the current are seen as the PSMIM concentration is increased so that the PSMIM weight is 5% of the weight of the silver (plot 202). Then there is a small decrease when the weight of the PSMIM is increased to 10% of the weight of the silver (plot 203).

A run in which the PSMIM weight was 20% of the weight of the silver was also performed. The cell showed a small current, but analysis of the exit stream did not show significant CO₂ conversion.

These results demonstrate that the addition of an ionomer containing an imidazolium to the cathode catalyst layer enhances the performance of a CO₂ electrolyzer and the PSMIM polymer is therefore a Helper Polymer.

U.S. patent application Ser. No. 15/158,227 (now U.S. Pat. No. 9,945,040) provides a number of other examples. The data in the '227 application indicates that polymers containing positively charged cyclic amines can also act as Helper Polymers.

Example 2: Stacks

Example 1 used a single cell, but commercial designs will use a stack 300 where multiple cells are interconnected as illustrated in FIG. 6. The stack consists of a number of cells 301, 302, 303 and 304. Each cell has an anode 311, 312, 313 and 314, respectively, a cathode 321, 322, 323 and 324, respectively, and an ion-conducting membrane 331, 332, 333 and 334, respectively, interposed between the anode and the cathode. There are electrical connections 340, 341, 342 between (i) cathode 321 and anode 312, (ii) cathode 322 and anode 313, and (iii) cathode 323 and anode 314. Electrical potential is provided between anode 311 and cathode 324.

The figure only shows one example. There can be between 2 and 1000 cells in the stack.

Multiple arrangements of power are possible. In one case, power is provided to the ends of the stack. In a second case, power is provided to individual sections of the stack so that there is a source of potential between the cathode of one cell in the stack and the anode of a different cell in the stack.

The design also includes examples where the anode of one cell is in electrical contact with the cathode of an adjacent cell. The design also includes examples where the anode of one cell is in electrical contact with the cathode of a different, non-adjacent, cell in the stack.

The stack includes a means to feed gaseous CO₂ with negligible liquid into the cathode and means to feed a liquid electrolyte such as dilute potassium bicarbonate into the anode. This differs from conventional electrochemical stacks where either (i) liquid electrolyte is fed into both sides of the stack, (ii) gas is fed into both sides of the stack, and/or (iii) a non-conductive liquid such as deionized water is fed into one or both of the sides.

The ion conduction path between two adjacent anodes is at least 3 cm. It also is at least 10 times and preferably at least 100 times the membrane thickness.

The example given above is illustrative and is not meant to be an exhaustive list of all possible embodiments, applications or modifications of the invention. Thus, various modifications and variations of the described methods and systems of the invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in connection with specific embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in the chemical arts or in the relevant fields are intended to be within the scope of the appended claims.

The disclosures of all references and publications cited above are expressly incorporated by reference in their entireties to the same extent as if each were incorporated by reference individually.

While particular elements, embodiments and applications of the present invention have been shown and described, it will be understood that the invention is not limited thereto since modifications can be made by those skilled in the art without departing from the scope of the present disclosure, particularly in light of the foregoing teachings. 

What is claimed is:
 1. An electrochemical device for converting CO₂ to a reaction product, the device comprising an electrolyzer stack, wherein the stack comprises at least two electrochemical cells, wherein each cell comprises: (a) an anode comprising a quantity of anode electrocatalyst; (b) a cathode comprising a quantity of cathode electrocatalyst; (c) a source of CO₂ directed to said cathode; (d) a membrane interposed between said anode and said cathode, wherein: (i) said cathode electrocatalyst is in the form of unsupported particles or particles supported on an electrically conductive support; (ii) said particles have an average size between 0.6 nm and 100 nm; and (iii) said cathode electrocatalyst converts CO₂ to a carbon-containing reaction product.
 2. The electrochemical device of claim 1, wherein said membrane has an average thickness and the shortest ion conduction path between anodes of different cells in the stack is at least 10 times the average membrane thickness.
 3. The electrochemical device of claim 2, wherein the shortest ion conduction path between anodes of different cells in the stack is at least 100 times the average membrane thickness.
 4. The electrochemical device of claim 1, wherein the shortest ion conduction path between anodes of different cells in the stack is at least 3 cm.
 5. The electrochemical device of claim 1, further comprising a conduit fluidly connecting the anode of one cell in the stack to the anode of a different cell in the stack, and a source of liquid electrolyte directed to said conduit.
 6. The electrochemical device of claim 1, further comprising an electrical connection between the anode of one cell in the stack and the cathode of a different cell in the stack.
 7. The electrochemical device of claim 6, further comprising a source of potential between the cathode of the one cell in the stack and the anode of a different cell in the stack.
 8. The electrochemical device of claim 1, further comprising a conduit fluidly connecting the cathode of one cell in the stack to the cathode of a different cell in the stack, said source of CO₂ directed to said conduit.
 9. The electrochemical device of claim 8, wherein said CO₂ is in gaseous form.
 10. The electrochemical device of claim 1, wherein said membrane is a polymer electrolyte membrane.
 11. The electrochemical device of claim 10, wherein said membrane is an anion exchange membrane.
 12. The electrochemical device of claim 1, wherein the average particle size of said particles is between 0.6 nm and 40 nm.
 13. The electrochemical device of claim 1, wherein said electrocatalyst comprises at least one of V, Cr, Mn, Fe, Co, Ni, Cu, Sn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Ir, Pt, Au, Hg, Al, Si, In, Tl, Pb, Bi, Sb, Te, U, Sm, Tb, La, Ce, and Nd.
 14. The electrochemical device of claim 13, wherein said Catalytically Active Element is selected from the group consisting of Pt, Pd, Au, Ag, Cu, Ni, Fe, Co, Ru and Rh.
 15. The electrochemical device of claim 1, wherein the reaction product comprises at least one of CO, HCO⁻, H₂CO, (HCOO)⁻, HCOOH, CH₃OH, CH₄, C₂H₄, CH₃CH₂OH, CH₃COO⁻, CH₃COOH, C₂H₆, (COOH)₂, (COO⁻)₂, and CF₃COOH.
 16. The electrochemical device of claim 15, wherein said reaction product is one of formic acid (HCOOH) and carbon monoxide (CO).
 17. The electrochemical device of claim 1, wherein said membrane comprises positively charged amines.
 18. The electrochemical device of claim 17, wherein said positively charged amines are imidazoliums or pyridiniums. 